Low molecular weight methacrylic acid ester polymers



' Patented June 11, 1940 I I UNITED STATES PATENT OFFICE LOW MOLECULAR WEIGHT ME'I HACRYLIC ACID ESTER POLYMERS .Daniel E. Strain, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation oi Delaware No Drawing. Application August 21, 1931, Serial No. 160,269

1 Claim. (Cl. 260-32) This invention relates to a process for obtaining lower the molecular weight of the polymer prolow molecular weight polymers and primarily to duced. Furthermore, the catalyst concentration low molecular weight polymeric esters of acrylic likewise is a major factor in the preparation of and methacrylic acids. low molecular weight polymers, for, at any given An object of the present invention is to protemperatu e. th molecular W t of e P y e vide a process for the preparation of low molecular varies inversely as the concentration of the catweight esters of polymeric acrylic and methacrylic y t. acid, which give solutions of low viscosity and Benzeyl peroxide, all extensively used pe y high solids content. Another object of the inzat n a a ys r t s s f a ry i and vention is to provide a process wh i s h methacrylic acid, is relatively inactive in the dark 0 omeric compounds are polymerized in solution W s in polymerizations a low p under suitable temperature, pressure and onatures. However, at temperatures in excess of centration conditions in order that a polymer and, more especially, in excess 0f having exceedingly low molecular weight is obthe effectiveness f a a y Such as benzeyl tained. A further object of the invention is to p o de in increasing h e of p y e a- I provide a correlation of polymerization condi- U011 d. Concurrently. the production of p ytions in order t obtain, an exceedingly 1 1 meric esters of low molecular weight becomes inular weight polymer in solution, which has a cleasingly evident. viscosity and solids content such that it maybe The elfects of temperature and benzoyl e de so used directly as a coating composition for spray- \concemratlons a illustrated by the data in 00 ing or brushing, oth objects and advantages Tables I and II. Reductions in molecular weight, of the invention win h r i ft appear. as the result of increased temperature, are ap- I have found that various factors influence the parent from the ve c and uctio solution polymerization of the esters of methdue to increased, benzoyl Peroxide concentration,

2 acrylic acid, among hi h are temperature of (catalyst concentration is expressed in weight per 05 polymerization, concentration of catalyst used, cent, based monomer) from the horizontal M concentration of monomerin the solvent in which columns in Table h data o which t ese polymerization is effected, and the nature of that ta es are C ed W a ed from work solvent. These factors all influence the molecu involving Solutions Comprising 450 Parts by V01- lar weight of the polymeric product. The moleclime of methanol, 450991178 y Volume Of Wa er 30 ular weight of the polymer is substantially a diand 100 parts by v u e f et yl y a e. rect measure of the viscosity of the resin in sowhich were heated at the indicated temperalution, i. e., for a given solids content the lowture throughout the period -for polymerization.

er the molecular weight of the resin th lower This combination of solvents does not dissolve the will be the viscosity of the solution containing ymer; but indicates the effectiveness of temit. Considered from the basis of solids content p r and cat y concentration n l w ri of a solution for a given viscosity the lower the the molecular Weight f the p y r zed resin. molecular weight of a resin the greater will be TABLE 1 the solids content of the solution containing that m resin H in ft primary reference will be Effect of temperature and catalyst concentration 40 made to molecular weight lowering, although it the molePulm' weigm methyl methacryl will be understood that the correlative effects of ate polymerized in volume'percent methanol solids content and viscosity will be included. As water a result of my investigations I have found that Molecular Weight o ds)! esters of acrylic and methacrylic acid can be a I a 46 polymerized to resins having exceptionally low p a u 0.0% 0.1% 0. 5% 1.0%

molecular weights and consequently these resins catalyst catalyst can be dissolved in large amounts in many, .or-

ganic solvents to give low viscosity solutions, if 33;; ff 1?; 5, 3 #5 m the factors above referred to are controlled with P i 5; 50

in certain limits. 1 a

When polymerizations are conductedin solu- T e a v i mat Could e p ifi d by 1 tion to produce low molecular weight polymers, similar experiments carried out in other liquids the higher the temperature of polymerization, the and also in-solvents for both monomer and poly- ;5 more rapid will. be thepolymerizatlon and the mer, but the trend is the same in all cases. '55

cation of Fikentschers and Staudingers equations as illustrated in Table II.

TABLE II is used as the solvent in 65 C. catalyst-free polymerizations (Table IV).

TABLE IV Concentration efiect-methyl methacrylate polymerzzea in 95% ethanol Viscosity and molecular weight of methyl meth- P t g gk g i t p ly 4 crash monomer thogsands) Molecular 75 Viscosity (poises) Relative k Intrinsic weight 77 6g./l00 co. in dioxan viscosity viscosity (Sta'udinger's 90 equation) 10 0 052 o 594 31 600 The concentration effect is also observed in 100 01033 1 741000 polymerizations using benzoyl peroxide in 95% 1 000 0.109 2.30 124 000 o 101000 133 338 000 ethanol at 65 C., (Table V). TABLE V Column 1 gives the viscosity in poises (25 C.) of dioxan solutions containing 5 grams of resin per 100 cc. of solution. Column 2 gives the ratio of the viscosity of the solution to the viscosity of the solvent taken as 0.0117 poise. Column 3 is Fikentschers viscosity constant as calculated from the equation where nr is the relative viscosity and c is the concentration. Column 4 gives the estimated intrinsic viscosity for very dilute solutions, the extrapolation being made with Fikentschers equation (In H. l ikentscher, Cellulosechemie, 13. 53-74 (1932).) Column 5 gives the molecular weights as calculated from the intrinsic viscosity by Staudingers method using the constants given by Staudinger in a paper on polyacrylic esters. (In H. Staudinger, Ann., 502, 201 (1933).) Molecular weights thus obtained are roughly 64% as great as those obtained by the application of Staudingers equation using viscosities determined at concentrations involving only 0.02 to 0.06 gram of polymer per 100 cc. of solution. Molecular weights from the more dilute solutions probably more nearly approach the true values. However, due to the assumptions involved, any molecular weights based on viscosity measurements are relative in nature and of use only for comparison with values determined in the same manner.

I have also found that when the concentration of the monomer is varied in a given solvent the molecular weight of the polymer varies directly with the monomer concentration. In a group of catalyst-free polymerizations carried out at 70 C. in a 50 volume per cent methanol-water mixture, data were obtained as given in Table III.

TABLE III Molecular weight (in thousands) Percent 11101101118! The same effect is observed when ethanol I absence of polymerization catalysts.

Concentration efiectmethyl methacrylate polymerized in 95 ethanol using 0.1% catalyst (based on the monomer) The data oi. Tables III, IV, V illustrate conclusively that the concentration of the monomer in solution determines to no small extent the molecular weight of the polymeric resin obtained.

In addition to the above conditions I have found that various solvents differ considerably in their influence on the molecular weights of polymers produced in them. Table VI gives data on the molecular weights obtained when 20% solutions of methyl methacrylate were polymerized in a number of solvents at 65 C. in the The table likewise shows that as polymerization proceeds the molecular weight of polymer formed continuously decreases as the yield of polymer increases.

TABLE VI Polymerization data for 20% methyl methacrylate solutions in various solvents Mol.wt./i00() Yield at the hours at the hours Solvent Acetone 73 0.. 78.5 75 Dioxan 98 40 37 .35 Ethylene chloride 63 75 54 Butylacetate... 86 4i Methoxyethanol... 81 07 50 4B 4b Methylene chloride 78 Ethylacetate 58 95% 75 75 $3: 96 166 Benzene 2i 95 The above considerations indicate the effectiveness of the temperature of polymerization, the concentration of catalyst, concentration oi monomer in the solution, wherein polymerization is to be effected. and the type of solvent used. Individually, each of these conditions has a decided effect on the lowering of the molecular weight of the estersof acrylic and methacrylic acid; combined, they have the ability of producing polymeric resins of such low molecular weight that they can be. dissolved in solvents to give a solids content of resin ranging from 30 to 60% by weight with viscosities ranging from 0.2 to 2 poises at 25 0. Polymeric methyl methacrylate, for example, may be prepared in accord with my invention to give a solution containing from 30 to of the polymer with a viscosity ranging from 0.2 to 2.0 poises at 25 C. This makes it possible to utilize these esters for applications in the lacquer industry, wherein it is absolutely necessary for commercial exploitation that the solids content of a lacquer be sufliciently high to obtain good covering and adequate protection by the minimum number-of lacquer coatings, and the viscosity be such that the solution may be easily applied by dipping, brushing or spraying.

Coating compositions are extensively applied by spraying and I have found that polymeric esters of acrylic and methacrylic acids, especially methyl methacrylate, of high molecular weight, even though dissolved to give a solution of spraying viscosity. will cobweb, i. e., threads will form between the spray gun and the work with the result that a rough, unacceptable coating, except for special purposes, is obtained. With low molecular weight polymers the "cobwebbing is eliminated and with resins having a viscosity between 0.3-0.7 poise at 25 C. excellent coatings can be applied. For desirable brushing viscosities those ranging between 1.5 to 2.0 poises at 25 C. are preferred.

Solutions having a solids content of 30 to 00% of resin give excellent brushing and spreading characteristics.

To obtain the lowest possible molecular weight polymers it is necessary, I have found, to carry Gil out the polymerization at temperatures in excess oi! C. and, preferably, between and 100 C.

tor methyl methacrylate and similar low-boiling monomeric esters and derivatives of acrylic and methacrylic acids such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the nitriles of acrylic and methacrylic acids. Temperatures well in ex cess of 100 0., however, may be employed especially when monomeric esters, e'. g., propyl methacrylate, butyl methacrylate, isobutyl methacrylate and the higher alcohol esters of methacrylic acid, are polymerized and particularly those which have boiling points above 100 C. The catalyst concentration should be at least 0.1%, based on the weight of monomer and, preferably, from 0.5 to 2% or higher, it being understood that the catalyst has essentially the equivalent activity of benzoyl peroxide, i. e., a given weight of catalyst will afiect the molecular weight during polymerization to the same extent as the same weight of benzoyl peroxide. in the event that the catalyst used has a lower activity considered by this measure, proportionately larger quantities thereof should be employed and, contrariwise, it the catalyst has a greater activity, proportionatcly smaller amounts will give substantially the same results. i

As has been indicated the type of solvent used is of considerable importance, and I have found that substantially anhydrous organic solvents which are solvents for both monomer and polymer are most suitable. Solvents which are well adapted for this purpose include: the ketones, such as acetone, cyclohexanone, and diisopropyl ketone (the latter being suitable for polymerizing the esters excepting methyl methacrylate); ethylene glycol monoethyl ether; the esters generally, e. g., methyl formate, ethyl acetate, isobutyl propionate, cyclohexyl acetate; the alkyl and aryl halides, ,e. g., methylene chloride, chloroform, ethylene dichloride, chlorobenzene; dioxan; benacne and toluene and for polymerizing butyl and isobutyl methacrylates, solvent naphtha. Table V; shows the effect of large amounts of waterwhich prevent the preparation of desirable molecular weight lowering.

The effectiveness of my process will be appreciated by the following examples in which parts are given by weight unless otherwise stated.

There are, of course, many toms of the invention other than these specific embodiments.

Example I .A solution containing 600 parts by weight of methyl methacrylate monomer, 1400 parts by weight of toluene and 12 parts by weight of benzoyl peroxide was placed in a flask fitted with a reflux condenser and heated for 7 hours This solution was suitable directly as prepared for coating or impregnating purposes by spraying, brushing or dipping. Films from it on baking to a solvent-free state are exceedingly hard, tough and have a good adhesion. According to solids determination the polymerization was essentially complete. The molecular weight of the polymer was found to be approximately 30,000. The solid polymer, after separation from the toluene, was found to be soluble in acetone, cyclohexanone, ethylene glycol monoethyl ether, methyl formate, ethyl acetate, butyl lactate, isobutyl propionate, cyclohexyl acetate, chloroform, methylene chloride, ethylene dichloride, chloroben'zene, dioxan, benzene, toluene, acetic acid, formic acid and isobutyric acid, and because of the low molecular weight of the polymer it is possible to get several times as much in solution at a workable viscosity than is possible with high molecular weight polymer.

Example II .-A solution containing 20 parts by weight of propyl methacrylate, 80 parts by weight of toluene, 0.4 part by weight of benzoyl peroxide were placed in a flask provided with a reflux condenser and heated for 6 hours at a temperature of approximately 92 C. At the end of this time the yield of polymer was substantially 95% and a 15% solution of this polymeric resin in toluene gave a viscosity of approximately 0.03 poise.

The low molecular weight polymers obtained" in accord with my invention are particularly well adapted for use in the preparation of lacquer compositions. It will be appreciated that for such compositions a resin should be highly soluble in the vehicle employed, and when my low molecular weight resins are used, they may be dissolved to give high solids content lacquers. l have found that films formed from lacquers containing the exceedingly low molecular weight polymers, say, 40,000 or lower, can be increased in toughness in order to give exceedingly tough and durable films by adding to the lacquer composition a plasticizing agent such, for example, as dibutyl phthalate, dicyclohexyl phthalate and dibutoxyhexyl phthalate, upon which a product will be obtained having exceptional and unusual protective powers. Various resinous and resin-like materials may also be used to modify the flexibility, toughness and hardness of films from these low molecular weight polymers, such, for example, as rosin, ester gum, phenol aldehyde resin, cellulose nitrate, vinyl chloride-vinyl acetate interpolymers, chlorinated rubber, chlorinated diphenyl resin, toluene sulfonamide-aldehyde resin, cumarone-indene resins, and asphalt.

My process is particularly adapted for low molecular weight polymers from the following monomeric compounds: the acid, nitrile, and esters of acrylic acid and, more particularly, the methyl, ethyl, propyl, butyl, isobutyl, octyl, tertiary amino ethyl, tertiary amino methyl, and higher acrylates are all subject to my improved process. Resins of low molecular weight may likewise be obtained from the acid, nitrile and esters of methacrylic acid and, more particularly, methyl, ethyl, npropyl, n-butyl, isobutyl, octyl, tertiary amino methyl, tertiary amino ethyl, cetyl, and the higher alkyl methacrylates. Moreover, mixtures of monomerlc compounds may .be similarly treated, e. 3., mixtures of dissimilar esters of acrylic acid, or esters of methacrylic acid; esters of acrylic acid with esters of methacrylic acids; esters of acrylic acid or esters of methacrylic acid with vinyl chloride, vinyl acetate or other poiymerizable compounds which form interpolymers,

From a consideration oi the above specification, it will be realized that many changes may be made in the details therein given without sacri- 1 flcing any of the advantages derived therefrom or departing from the scope oi the invention.

I claim: v

A process of preparing a low molecular weight polymer of a butyl methacrylate which comprises polymerizing the ester in solvent naphtha, at a temperature in excess of 100 C. and with a catalyst concentration of from 0.5 to 2.0% benzoyl peroxide, based on the weight of monomeric compound present, the solution prior to polymerization containing less than 30% monomer, the polymerization being continued until a polymer is obtained which will dissolve in toluene to give a liquid having a solids content of from 30-60% and a viscosity of from 0.2 to 2.0 poises at 25 C.

DANIEL E. STRAIN. 

